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April 18, 1961 J. F. ROSS ET AL PROCESS FOR THE PURIFICATION OF 2,4-DIKETONE CHELATING AGENT-CONTAMINATED POLYMERIZATION HYDROCARBON DILUENTS Filed Nov. 10, 1958 N E E N a 5'5 ":8 8 mm 99 x0:

l l [I 5 m1 J E m uJ- x 2 2 2 1 P g (D g z 0 l F- LL] (0 r zw t 6% DC LU 25 2 n domes Francis Ross Bruce R. Tegge Inventors Leon Clifford Kenyon,dr.

By Y CW A'ri'orney United States Patent PROCESS FOR THE PURIFICATION OF 2,4-DIKE- TONE CHELATING AGENT-CONTAMINATED POLYMERIZATION HYDROCARBON DILUENTS Filed Nov. 10, 1958, Ser. No. 773,075

6 Claims. (Cl. 260674) .This invention relates to the purification of diluents used in the low-pressure polymerization of olefins and more particularly relates to the purification of contaminated recycle diluents. 7

' Diluents recovered from the low-pressure polymerization of olefins are usually contaminated with chelating agents such as acetylaceton'e and diacetyl when these chelating agents are used to help remove catalyst residues from polymerization reaction mixtures. Additionally, C to C alkanols such as methanol, ethanol, isopropanol, and butanols areused to precipitate the polymer product from the hydrocarbon diluents which are usually used in the polymerization reaction. Reuse of the hydrocarbon diluent requires the removal of substantially all of the above chelating agents and alkanols. Most of the'alkanol can be removed by rectifying the alkanol-diluent mixture. However, significant quantities of the contaminating chelating agent will be found in the hydrocarbon diluent stream from the rectifier, particularly When the hydrocarbon diluent is an aromatic hydrocarbon such as xylene. One technique previously proposed to remove chelating agents from the hydrocarbon diluent stream was by the use of adsorption with alumina, silica gel, molecular sieves, etc. However, the adsorption technique gives rise to formidable process problems, particularly with reference to the liquid phase adsorber operation, the high temperatures regeneration of the adsorbent and the stability adsorbent material.

It has now been found that organic chelating agents such as acetylacetone and diacetyl can be removedfrom hydrocarbon diluents obtained from the'rectification of diluent-alkanol mixtures by treatment of the contaminated diluent with a dilute caustic solution followed'by drying of the diluent by azeotropic distillation.

The diluents purified by the present invention are aliphatic hydrocarbons such as isopentane,. cyclohexane, heptane, and the like, and aromatic hydrocarbons such as benzene, toluene xylene and the like. The aromatic hydrocarbons are employed as the diluents of choice in the polymerization of propylene and higher alpha olefins.

While it does not comprise part of the invention, a general description of the low-pressure polymerization process will be provided for the purpose of completeness. The low-pressure polymerization reaction is carried out by contacting an olefin feed stream containing the olefins to be polymerized with a polymerization catalyst at a temperature in the range of 0 to 100 C. The polymerization catalysts are generally systems made up of a mixture of reducible heavy transition metal compounds such as titanium tetrachloride, titanium trichloride, and titanium trichloride cocrystallized with aluminum chloride, and a reducing agent such as an organo-metallic compound, e.g triethyl aluminum and diethyl aluminum chloride. Other reducing agents such as alkali and alkaline earth metals andhydrides and alloys of aluminum hydrides and the like can also be used. The reducing metal compounds most often used are the halides, acetylacetonates. and

other compounds of the metals of groups IV through VI and VIII of the periodic table. A batch or continuous olefin polymerization process can be used. Atmospheric pressures are' usually adequate for diluents normally liquid at atmospheric pressure at polymerization temperatures, but the polymerization reaction can be carried out at sub or supra atmospheric pressures. When the polymerization reaction has progressed to the desired extent, from about 0.2 to 2 parts of a C to C alkanol such as methanol, isopropyl alcohol, and n-butyl alcohol per part by weight of reaction mixture is added with a chelating agent such as a 2,4-diketone, e.g. acetylacetone or diacetyl to complex the catalyst prior to filtration or other physical removal of the precipitated polymeric product. The polymeric product can then be treated with hydrochloric acid, water washed and then dried orwashed With additional alcohol and dried in the absence of Water. The hydrocarbon diluent-alkanol filtrate mixture which is separated from the polymeric product and which contains the chelating agent is then rectified into a substantially alkanol fraction and a substantially hydrocarbon diluent fraction. The latter fraction is then purified by the process of the invention. I

To more fully understand the invention, reference Will now be made to the drawing which is a diagrammatic flow plan of the diluent purification process in accordv ance with this invention. For clarity purposes, xylene is used as the polymerization diluent, acetylacetone is used as the chelating agent, and methanol as the precipitating alkanol. carbon diluents and other organic alkanols and chelating agents in accordance with the invention can be used in place of xylene, acetylacetone, and methanol, respectively.

Contaminated xylene from a xylene-methanol rectifier is introduced through line 1 into mixer 4 together with dilute caustic which is introduced through line 2 by although potassium hydroxide can likewise be used.

a From 10 to 200 wt. percent caustic solution is used based of the chelating agent and its eif ects on the life of the on the xylene feed. Mixer 4 isQpreferably an orifice mixer although other types of efiicient mixers can equally well be utilized. The xylene-aqueous caustic mixture is then 7 layer from settling tank 6 is passed through line 10 to mixer 12 together with wash water introduced in line 11. In general, from 5 to 100 wt. percent wash water is used based on the weight of xylene introduced to mixer 12. Mixer 12 is preferably an orifice mixer although like mixer '4 other types of mixers can be used. The xylene-wash water mixture is then passed from mixer 12 through line 13 into settling tank 14. The temperature in settling tank 14 is maintained in the range of to 200 F.. The mixture is allowed to settle and a lower water layer is removed through line 15. The upper xylene layer is passed from settling tank 14 through line 16 into azeotropic drying tower 17. Azeotropic drying tower 17 is maintained at a temperature in the range of 200 to 350 F and at a pressure in the range of 1 to 50 p.s.i.g. depending on the hydrocarbon diluent used. The temperature and pressure are chosen to provide for efi'icient distillation. Distillate is removed through line 18 and passed into condenser drying tower preferably contains from 10 to 25 bubble- It is, of course, understood that other hydrocap plates. Xylene is removed through line 20 at the bottom of tower 17 and passed into kettle reboiler 21. Vaporized xylene from kettle reboiler 21 is returned through line 22 into drying tower 17. Essentially. an-

those skilled in the art without departing from the spirit and scope of the invention. 7

What is claimed is:

1. A process for purifying 2,4-diketone chelating hydrous xylene liquid is recovered from the kettle reboiler agent-contaminated, substantially alcohole free hydrothrough line 23. The kettle reboiler 21 is operated so carbon diluent selected from the group consisting of as to provide a xylene vapor return rate of from 10 to aliphatic hydrocarbons and single ring aromatic hydro- 100 wt. percent based on the feed xylene rate. carbons from a diluent-alkanol rectifier used to rectify It should be noted that the aqueous caustic solution liquid separated from a low pressure catalytic olefin polycontains sufficient causticto provide for a pH of 13 to 10 merization reaction mixture comprising the steps of 14 in the aqueous layer passed through line 7 from washing said contaminated hydrocarbon diluent with settling tank 6. When the pH of this caustic solution aqueous alkali, separating said washed diluent from said is 14 it was found that substantially 160% of the acetyl aqueous alkali, washing said separated diluent with Water, acetone from the xylene layer is present in the aqueous separating the water washed diluent, passing the separated caustic phase. 15 diluent into an azeotropic drying tower, and separating The process will be better understood by reference a substantially pure hydrocarbon diluent therefrom. to the following example. 2. A process for purifying a 2,4-diket0ne chelating EXAMPLE agent-contaminate substantially alcohol free, single ring aromatic hydrocarbon diluent from a diluent-alkanol A xylene side stream from a methanol-xylene splitter rectifier used to rectify liquid separated from a low preswhich contained acetylacetone and methyl alcohol as irnsure catalytic olefin polymerization reaction mixture purities introduced during the treatment of a polypropylcomprising the steps of washing said contaminated hyene reaction mixture was introduced through line 1 in drocarbon diluent with aqueous alkali, separating said the apparatus schematically shown in the drawning. washed diluent from said aqueous alkali, washing said Aqueous alkali and feed xylene were introduced into separated diluent with water, separating the water washed mixer 4 at a 1:1 volume ratio. Wash water was introdiluent, passing the separated diluent into an azeotropic duced into mixer 12 at a rate of 12 wt. percent based drying tower, and separating a substantially pure hydroon the rate of xylene. The entire system was operated 7 carbon diluent therefrom. at about atmospheric pressure except in the azeotropic 3. The process of claim 2 wherein said aromatic hydrying tower where the overhead pressure was 4 p.s.i.g. drocarbon is xylene. The temperature in settling tank 6 was maintained at 4. The process of claim 2 wherein the organic chelatin 170 F. and in settling tank 14 at 140 F. The temagent is acetylacetone. perature of the overhead in line 18 was 300 F. Azeo- 5. A process for purifying a 2,4-diketone chelating tropic drying tower 17 contained 20 bubble-cap plates agent-contaminated substantially alcohol free hydrocarand was maintained at an average temperature of 300 bon diluent selected from the group consisting of aliphat- F. The following table gives the rates and compositions ic hydrocarbons and single ring aromatic hydrocarbons of the streams in various portions of the system. from a diluent-alkanol rectifier used to rectify liquid sep- Table Stream 1 2 9 11 15 16 23 Rate, Lbs/Hm X1 0.08 0.25 1,150 919.67 19. 6 110 110 1. 85 0.006 Acetylaceton 0. 70 Methyl Alcohol. 0. 01 O. 01 NaOH 1.10 0.80 0. 01 Sodium Acety Acetonate 0.83

Total 920. 71 22.10 21.32 110 110.26 1,151.85 919.68

C0ncen., p.p.m.:

Xylene Main 3740 2, 360 Main Main Stream Stream Stream Water Main Main Main Main 1,600 5 Stream Stream Stream Stream Acetylaeetone 0 Methyl Alcohol 470 NaOH 37, 550 91 Sodium Acetyl Acetonat 38, 900

It can be seen from the above table and from the arated from a low pressure catalytic olefin polymerizaexample that substantially complete removal of acetylacetion reaction mixture comprising the steps of washing said tone and methanol from xylene are accomplished by the contaminated hydrocarbon diluent with aqueous alkali, process of the invention. Additionally, only 5 ppm. of separating said washed diluent from said aqueous alkali, water are left in the purified xylene which is, of course, washing said separated diluent with water separating the suitable for recycling to the polymerization process. water washed diluent, passing the separated diluent into It should be noted that if the acetylacetone is not rean azeotropic drying tower, separating a substantially moved from the contaminated xylene stream and azeopure hydrocarbon diluent therefrom, condensing distiltropic ,distillation is attempted to purify the xylene, the late from the azeotropic drying tower and recycling it to acetylacetone will continue to increase in concentration the aqueous washing step. in the tower to such an extent that the tower is not 0p- 6. A process for purifying a 2,4-diketone chelating erative unless some of the diluent is continuously or agent-contaminated substantially alcohol free hydrocarintermittently removed to decrease the concentration of bon diluent selected from the group consisting of aliphatthe acetylacetone in the system. The removal of part of ic hydrocarbons and single ring aromatic hydrocarbons the diluent for this purpose is, of course, wasteful, time from a diluent-alkanol rectifier used to rectify liquid sepconsuming, and expensive. arated from a low pressure catalytic olefin polymeriza- Modifications of the above process can be made by 76 tion reaction mixture comprising the steps of washing 5 6 said contaminated hydrocarbon diluent with aqueous altower, and separating a substantially pure hydrocarbon kali containing from 0.2 to 20 wt. percent alkali therein, diluent therefrom. mixing the contaminated diluent with the aqueous alkali in an amount sufficient to remove substantially all or- 1 References Cited in the file of this Patent ganic impurities from said diluent, separating said washed 5 UNITED STATES PATENTS diluent from said aqueous alkali, washing said separated 1 diluent with water, separating the water washed diluent, 1,741,305 Jaeger Dec. 31, 1929 passing the separated diluent into an azeotropic drying 2,809,211 Keunecke et al. Oct. 8, 1957 

1. A PROCESS FOR PURIFYING 2,4-DIKETONE CHELATING AGENT-CONTAMINATED, SUBSTANTIALLY ALCOHOLE FREE HYDROCARBON DILUENT SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBONS AND SINGLE RING AROMATIC HYDROCARBONS FROM A DILUENT-ALKANOL RECTIFIER USED TO RECTIFY LIQUID SEPARATED FROM A LOW PRESSURE CATALYTIC OLEFIN POLYMERIZATION REACTION MIXTURE COMPRISING THE STEPS OF WASHING SAID CONTAMINATED HYDROCARBON DILUENT WITH AQUEOUS ALKALI, SEPARATING SAID WASHED DILUENT FROM SAID AQUEOUS ALKALI, WASHING SAID SEPARATED DILUENT WITH WATER, SEPARATING THE WATER WASHED DILUENT, PASSING THE SEPARATED DILUENT INTO AN AZEOTROPIC DRYING TOWER, AND SEPARATING A SUBSTANTIALLY PURE HYDROCARBON DILUENT THEREFROM. 